Catalytic solid usable for the stereospecific polymerization of alpha-olefins, process for preparing it and process for polymerizing alpha-olefins in its presence

ABSTRACT

Catalytic solids based on titanium trichloride complex, usable for the stereospecific polymerization of alpha-olefins, obtained by heat treatment, in the presence of a halogenated activating agent, of the liquid material resulting from bringing TiCl 4 , pretreated with an electron-donor compound, into contact with a composition (C) corresponding to the general formula 
     
         AlR.sub.p (Y) .sub.q X .sub.3-(p+q) 
    
     in which 
     R represents a hydrocarbon radical or a hydrogen atom; 
     Y represents a group chosen from --OR&#39;, --SR&#39; and --NR&#39;R&#34;, in which R&#39; and R&#34; each represent a hydrocarbon radical or a hydrogen atom; 
     X represents a halogen; 
     p is an arbitrary number such that 0&lt;p&lt;3; and 
     q is an arbitrary number such that 0&lt;q&lt;3; the sum (p+q) being such that 0&lt;(p+q)≦3. 
     These catalytic solids of controllable porosity permit the production of a wide range of propylene polymers, in particular the propylene and ethylene copolymers known as &#34;block&#34; copolymers.

The present invention relates to a catalytic solid usable for thestereospecific polymerisation of alpha-olefins, a process for preparingthis solid and a process for the polymerisation of alpha-olefins in thepresence of this solid.

It is known to polymerise alpha-olefins, such as propylene,stereospecifically using a catalytic system comprising a solidconstituent based on titanium trichloride and an activator comprising anorganometallic compound such as an alkylaluminium chloride.

In the patent BE-A-780758 (SOLVAY & Cie) particles of titaniumtrichloride complex have been described, the use of which in thepolymerisation of alpha-olefins is particularly advantageous. Theseparticles are characterised by their particular structure. In fact, theyconsist of an agglomerate of microparticles which are themselvesextremely porous. The consequence of this is that these particles have aparticularly high specific surface area and porosity.

This particular structure leads, on polymerisation, to exceptionalperformance. Because of the porosity of the microparticles developedessentially in the pores having radii of less than 200 Å, the catalyticactivity is so high that it is possible to carry out the polymerisationunder conditions such that the catalytic residues no longer have to beremoved. Moreover, given that these particles are in the shape ofregular large spheres, the polymer obtained is likewise in the form ofregular spherical particles. The consequence of this is that it has ahigh apparent specific weight and that it has a very good pourability.

However, these particles are not suitable for the production of highimpact-strength block copolymers (known as "high impact grades")obtained by incorporating, in a propylene homopolymer prepared in afirst step, significant amounts of a propylene/ethylene elastomerprepared in a second step. In fact, the high density and the porosity,essentially confined in the very small pores, of these particles oftitanium trichloride complex lead to a homopolymer, the low porosity ofwhich, in its turn, does not permit the incorporation therein of largeamounts of elastomer, thus giving rise to caking problems which are themore acute the larger the amount of elastomer to be incorporated. Theseproblems are particularly disagreeable in the polymerisation processescarried out using the most recent techniques, that is to say in themonomer kept in the liquid state or in gas phase.

An attempt has been made to overcome these problems by producing thesecopolymers in the presence of solid catalytic constituents characterisedby a porosity of not less than 0.08 cm³ /g in the zone of pore radii ofbetween 200 and 15000 Å (Patent Application EP-A-0202946 (SUMITOMOCHEMICAL)). The preparations of the catalytic constituents described inthis application and having this characteristic are, however, complexand the operating method chosen predetermines the porosity obtained.

It has now been found that catalytic solids which are of controllableporosity and therefore are capable of being used to prepare a wide rangeof alpha-olefin polymers may be prepared in a simple manner.

The present invention relates, accordingly, primarily, to catalyticsolids based on titanium trichloride complex obtained by heat treatment,in the presence of a halogenated activating agent, of the liquidmaterial resulting from bringing TiCl₄, pretreated with anelectron-donor compound, into contact with a composition (C)corresponding to the general formula

    AlR.sub.p (Y) .sub.q X .sub.3-(p+q)                        (I)

in which

R represents a hydrocarbon radical;

Y represents a group chosen from --OR', --SR' and --NR'R", in which R'and R" each represent a hydrocarbon radical or a hydrogen atom;

X represents a halogen; p is an arbitrary number such that 0<p<3; and qis an arbitrary number such that 0<q<3, the sum (p+q) being such that0<(p+q)≦3.

In the formula (I) of the composition (C), R, R' and R" are, in the casewhere they represent a hydrocarbon radical, generally each chosen,independently of one another, from:

straight-chain or branched alkyl radicals containing from 1 to 12 carbonatoms, for example the methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, n-amyl, isoamyl, n-hexyl, 2-ethylhexyl and n-octyl radicals;

alkenyl radicals containing from 2 to 12 carbon atoms, for example theethenyl, 1-butenyl, 2-butenyl, 2-penten-4-yl, 1-octenyl and 1-decenylradicals;

optionally substituted cycloalkyl radicals containing from 5 to 12carbon atoms, for example the cyclopentyl, cyclohexyl, methylcyclohexyland cyclooctyl radicals;

optionally substituted aryl radicals containing from 6 to 35 carbonatoms, for example the phenyl, tolyl, cresyl, xylyl, naphthyl and2,6-di-tert-butyl-4-methylphenyl radicals; and

arylalkyl radicals containing from 7 to 20 carbon atoms, for example thebenzyl radical.

In the formula (I), X is preferably chlorine; R is preferably chosenfrom the straight-chain or branched alkyl radicals containing from 2 to8 carbon atoms; Y is preferably chosen from the groups --OR' in which R'is an alkyl radical as defined above or an aryl radical as definedabove. A very particularly preferred radical R is the ethyl radical.Very particularly preferred radicals R' are ethyl and isoamyl radicals.

In the formula (I), p is preferably a number such that 1≦p≦2 and q ispreferably a number such that 0.1≦q≦2 and very particularly such that0.15≦q≦0.65.

The compositions (C) used to prepare the catalytic solids according tothe invention may be chemically defined compounds or mixtures ofcompounds. The formula (I) must therefore be regarded as an empiricalstructural formula representing the said compounds or, in the case ofmixtures, representing the average composition of the latter.

The compositions (C) used to prepare the catalytic solids according tothe invention may be prepared from organoaluminium compounds (A) ofgeneral formula

    AlR.sub.n X.sub.3-n                                        (II)

in which R and X have, respectively, the meanings given above withrespect to formula (I) and in which n is an arbitrary number such that0<n≦3, preferably such that 1≦n≦3.

The following may be mentioned as examples of compounds (A): alkylatedaluminium compounds, such as trialkylaluminiums, dialkylaluminiummonohalides and alkylaluminium dihalides and sesquihalides, in which thealkyl radicals are those defined and enumerated above.

Preferred compounds (A) are dialkylaluminium chlorides, veryparticularly diethylaluminium chloride.

For the preparation of the composition (C), the compound (A) may bebrought into contact with a compound (B) chosen from the compounds ofgeneral formula:

    AlR.sub.m (Y) .sub.m' X .sub.3-(m+m')                      (III)

    YH                                                         (IV)

and from the oligomers of aluminoxane type which are in cyclic and/orlinear form and may be represented by the general formulae

    --[Al(R)--O]--.sub.n'+2                                    (V)

and

    R.sub.2 Al--O--[Al(R)--O].sub.n' --AlR.sub.2               (VI)

In the above formulae (III), (V) and (VI), R, Y and X have,respectively, the meanings given above with respect to formula (I). Informula (III), m is an arbitrary number such that 0≦m<3, preferably suchthat 0.5≦m≦1.5; m' is an arbitrary number such that 0<m'≦3, preferablysuch that 1≦m'≦2; the sum (m+m') being such that 0<(m+m')≦3.

In the formulae (V) and (VI), n' is an integer, generally between 2 and50.

Examples which may be mentioned of compounds (B) of formula (III) are:trialkoxyaluminiums, alkoxyalkylaluminiums, alkoxyaluminium halides andalkylalkoxyaluminium halides. Preferred compounds (B) of formula (III)are alkylalkoxyaluminiums and their chlorides, very particularlydiethylethoxyaluminium and ethylethoxy- and ethylisopentoxyaluminiummonochlorides. Examples which may be mentioned of compounds (B) offormula (IV) are: alcohols, thioalcohols, phenols, thiophenols andsecondary amines. Preferred compounds of formula (IV) are aliphaticalcohols, for example methanol, ethanol, propanol, isopropanol, butanol,isobutanol, pentanol, 2-methyl-1-pentanol (isoamyl alcohol), hexanol,2-ethylhexanol and octanol. Very particularly preferred alcohols areethanol and isoamyl alcohol.

Examples which may be mentioned of compounds (B) of formula (V) and (VI)are: methyl-, ethyl- and butylaluminoxanes.

The compound (A) and the compound (B) defined above are brought intocontact in the proportions appropriate for obtaining a composition (C)corresponding to the above formula (I). In order to do this, accountmust be taken of the respective natures of the compounds (A) and (B)used, as well as any chemical reactions which may take place duringtheir mixing.

The precise determination of the amounts of compounds (A) and (B) to beused may, accordingly, necessitate a few preliminary routine tests.

A particularly preferred and simple operating method for the preparationof the composition (C) comprises bringing a compound (A) which is analkylated aluminium compound into contact with a compound (B) which isan aliphatic alcohol, in a ratio between the aluminium contained in thecompound (A) and the hydrocarbon radical contained in the compound (B)of between 1/0.1 and 1/3. This bringing into contact induces an at leastpartial chemical reaction between these compounds, giving rise, inparticular, to the formation of an ═Al--OR' bond and being accompaniedby an evolution of gas.

The other general conditions for the preparation of the composition (C)are not critical.

In general, the reaction is carried out in liquid phase, for example bymixing together the compound (A) and the compound (B) at least one ofthese frequently being liquid under normal temperature and pressureconditions. It is also possible to carry out the reaction in thepresence of an inert hydrocarbon diluent, generally chosen from liquidaliphatic, cycloaliphatic and aromatic hydrocarbons, such as the liquidalkanes and isoalkanes and benzene. In this case, the composition (C) isgenerally present in this diluent in a proportion of 1 to 50% by volume,preferably of 5 to 30% by volume.

The compounds (A) and (B) may be brought into contact at temperatures ofbetween about 0° and 90° C., preferably between 20° and 50° C.approximately and their mixture kept for a time sufficient to allow anypossible chemical reaction between them to take place completely,generally for between 5 minutes and 48 hours, preferably between 2 and24 hours.

For the preparation of the catalytic solids according to the invention,the composition (C) is brought into contact with TiCl₄, which is itselfpretreated with an electron-donor compound. This electron-donor compoundis generally chosen from organic compounds comprising one or more atomsor groups having one or more free electron pairs capable of ensuringcoordination with titanium. These compounds have from 1 to 30 carbonatoms per electron donor atom or group.

The following may be mentioned amongst the atoms capable of giving oneor more electron pairs: atoms of non-metals of groups V and VI of thePeriodic Table, such as, for example, oxygen, sulphur, nitrogen,phosphorus, antimony and arsenic.

The following may be mentioned as representative examples of compoundscontaining groups capable of giving one or more electron pairs: ethers,thioethers, thiols, phosphines, stibines, arsines, amines, amides,ketones and esters.

Preferably, the electron-donor compound is chosen from the groupcomprising aliphatic ethers, and more particularly from those in whichthe aliphatic radicals contain from 2 to 8 carbon atoms, preferably 4 to6 carbon atoms. A typical example of an aliphatic ether giving very goodresults is diisoamyl ether.

The general conditions for the treatment of TiCl₄ with theelectron-donor compound are not critical, provided that they give riseto complexation of the TiCl₄ by the electron-donor compound. In general,the reaction is carried out in liquid phase, by adding theelectron-donor compound, optionally dissolved in an inert hydrocarbondiluent as defined above, to the TiCl₄, which is itself in pure liquidform or dissolved in such a diluent. When use is made of a diluent, theTiCl₄ is generally present therein in a proportion of 1 to 50% byvolume, preferably of 5 to 30% by volume. The treatment of TiCl₄ withthe electron-donor compound is carried out at a temperature which isgenerally between 0° C. and the boiling point of TiCl₄ or of thediluent, if such is used, preferably between 5° and 40° C.

The molar ratio between TiCl₄ and the electron-donor compound may varywithin wide limits. It is generally between 0.01 mol and 20 mol of TiCl₄per mole of electron-donor compound, preferably between 0.2 and 10 molper mole. The best results have been obtained for molar ratios betweenTiCl₄ and the electron-donor compound of between 0.3 and 5.

The general conditions for bringing TiCl₄ pretreated with theelectron-donor compound as described above (hereinafter abbreviated to"pretreated TiCl₄ ") into contact with the composition (C) are also notcritical, provided that they lead to the formation of a liquid materialwhich is substantially homogeneous and free from solid. In general, thecomposition (C), in pure liquid form or in dilute form in an inerthydrocarbon diluent as defined above, is introduced into the pretreatedTiCl₄, which is itself in liquid form or diluted in an inert hydrocarbondiluent which may be identical to or different from that in which thecomposition (C) has optionally been diluted.

The composition (C) and the pretreated TiCl₄ are brought into contact inrespective amounts such that an at least partial reaction of the TiCl₄is produced without substantial concomitant production of solidprecipitate. To this end, the amount of composition (C) brought intocontact with the pretreated TiCl₄ is such that the atomic ratio betweenthe aluminium contained in the composition (C) and the titaniumcontained in the pretreated TiCl₄ is generally between 0.05 and 10,preferably between 0.1 and 8; the best results are obtained if thisratio is between 0.2 and 2.

The temperature at which the composition (C) and the pretreated TiCl₄are brought into contact is generally between 0° and 60° C., preferablybetween 10° and 40° C.

For the preparation of the catalytic solids according to the invention,the liquid material obtained as indicated above must be converted intosolid particles. To this end, the said material undergoes a heattreatment in the presence of a halogenated activating agent.

The general conditions for the heat treatment of the liquid material arenot critical provided that this treatment induces substantialprecipitation of particles of solid based on titanium trichloride. Theseconditions are generally also chosen so as to lead to substantiallyspherical particles which are of uniform particle size and have anaverage diameter of between 5 and 150 microns (μm), preferably between10 and 100 μm.

To this end, the liquid material is brought progressively from atemperature higher than the temperature at which the composition (C) isbrought into contact with the pretreated TiCl₄ to a temperature whichdoes not exceed the boiling point of the liquid material.

In general, the temperatures between which the liquid material is heatedrange from about 20° to about 150° C., preferably from about 40° toabout 130° C. and very particularly from 80° to 120° C. approximately.

The duration of the heat treatment is generally between 5 and 150minutes, preferably between 20 and 120 minutes and very particularlybetween 30 and 75 minutes.

The heat treatment may be carried out by raising the temperature of theliquid material in a continuous manner or by observing one or moreplateaus during the rise in temperature.

Further details relating to the heat treatment of liquid materials,related to those defined above, may be found in particular in the U.S.Pat. No. 4,115,533 (MITSUBISHI CHEMICAL INDUSTRIES), the contents ofwhich are incorporated by reference in the present description.

According to the invention, the heat treatment of the liquid materialtakes place in the presence of a halogenated activating agent."Halogenated activating agent" is understood to denote all of the agentswhose presence contributes to the conversion of the reduced solidtitanium trichloride which forms during the heat treatment of the liquidmaterial substantially into the stereospecific violet form of thissolid.

These agents are generally chosen from inorganic halogenated compounds,organic halogenated compounds, hydrocarbylaluminium halides,interhalogen compounds and halogens. Amongst these agents, the followingmay be mentioned:

by way of inorganic halogenated compounds: metal and non-metal halides,such as titanium, vanadium, zirconium, aluminium, silicon and boronhalides, for example;

by way of organic halogenated compounds: halogenated hydrocarbons, suchas halogenated alkanes and carbon tetrahalides, for example;

by way of hydrocarbylaluminium halides: alkylaluminium dihalides inwhich the alkyl radical contains from 1 to 8 carbon atoms;

by way of interhalogen compounds: iodine chloride and iodine bromide,for example; and

by way of halogen: chlorine, bromine and iodine.

Examples of activating agents which are very suitable are titaniumtetrachloride, silicon tetrachloride, iodobutane, monochloroethane,hexachloroethane, chloromethylbenzene, carbon tetrachloride,ethylaluminium dichloride, iodine chloride and iodine. The best resultshave been obtained with titanium tetrachloride (TiCl₄).

The activating agent may be added to the liquid material at any timeduring the heat treatment; it may, for example, be added at the start ofthe heat treatment; it may also, in particular when plateaus areobserved during the rise in temperature, be added throughout the heattreatment, in particular during one of these plateaus.

When use is made of TiCl₄ as activating agent, this TiCl₄ mayadvantageously originate from a non-reduced excess of the initial TiCl₄from which the catalytic solids according to the invention are prepared.

The amount of activating agent used is expressed relative to the amountof titanium trichloride present in the liquid material. It is generallybetween 0.1 and 20 mol of activating agent per mole of titaniumtrichloride, preferably between 0.5 and 10 mol per mole. The bestresults have been obtained when the activating agent is used in aproportion of 1 to 5 mol per mole of titanium trichloride.

It has proved advantageous to subject the particles of solid based ontitanium trichloride complex resulting from the heat treatment of theliquid material described above to ageing, generally carried out at thetemperature reached at the end of the heat treatment, for a period ofgenerally between 15 minutes and 24 hours, preferably between 30 minutesand 5 hours.

The particles of solid based on titanium trichloride complex obtained bythe process described above are preferably separated from theirpreparation medium, for example by filtration, settling or centrifuging.They are preferably then washed using an inert hydrocarbon diluent ofthe same nature as those optionally used to prepare the catalytic solid.

As has been mentioned above, if the operating conditions for the heattreatment of the liquid material have been adjusted to this end, thesesolid particles have a generally substantially spherical shape, a narrowparticle size distribution and an average diameter of preferably between10 and 100 μm. Their titanium trichloride content is generally higherthan 50% by weight, preferably higher than 75% by weight, and theirelectron-donor compound content is generally less than 15% by weight,preferably less than 10% by weight, relative to the total weight of theparticles.

A considerable advantage of the invention lies in the fact that theporosity of the particles of catalytic solid may be controlled to alarge extent by the choice of certain operating conditions for theirpreparation. It has thus been found, in particular, that, all otherconditions remaining substantially unaltered, an increase in the contentof Y groups in the composition (C) leads to a modification of theporosity of the particles of catalytic solid and in particular to anincrease in the internal porosity of these particles generated by poreswhose radius is between 1000 and 15000 Å (hereinafter termed more simplyIPV). By virtue of the process for the production of catalytic solidsaccording to the invention, it is therefore possible to adjust theirporosity, in particular the IPV, from values as low as 0.02 cm³ /gapproximately up to values as high as 0.4 cm³ /g approximately.

It is also found that, all other conditions remaining substantiallyunaltered, an increase in the amount of composition (C) used leads, witha higher yield, to the production of particles of catalytic solid whichare of smaller size and have a smaller pore volume.

The increase in the porosity of the catalysts within the zone of poreradii under consideration leads in particular to alpha-olefin polymersof increasing porosity, which enables the incorporation therein of largeand increasing amounts of elastomeric products without encounteringadhesion problems.

Diverse variants may be applied to the processes, described above, forthe preparation of the catalytic solids based on titanium trichloridecomplex according to the invention without departing from the scope ofthe latter.

A first embodiment variant (a) consists in adding an organic orinorganic support (S), having a porous texture such that the particlesof solid based on titanium trichloride complex are deposited on thesurface of the support (S) or precipitate inside the pores of thelatter, to the mixture for the preparation of the catalytic solid basedon TiCl₃ complex, at any time but preferably before the heat treatmentof the liquid material. This addition may, for example, be carried outbefore bringing the pretreated TiCl₄ into contact with the composition(C).

In order to do this, supports (S) are generally used in which the porevolume is at least 0.1 cm³ /g and preferably at least 0.2 cm³ /g. Thispore volume generally does not exceed 3.5 cm³ /g, preferably does notexceed 2.5 cm³ /g and more particularly does not exceed 2.2 cm³ /g. Goodresults are obtained when the specific surface area of the supports (S)is larger than 1 m² /g. Most often, the specific surface area of thesesupports is less than 900 m² /g.

The supports (S) generally consist of particles larger than 5 μm in sizeand more particularly larger than 10 μm in size. In general, the size ofthe particles of the supports (S) is not larger than 350 μm andpreferably not larger than 200 μm.

Organic supports (S) which can be used are, for example, preformedpolymers such as styrene polymers and copolymers, vinyl chloridepolymers and copolymers, acrylic acid ester polymers and copolymers,polymers and copolymers of olefins containing from 2 to 18 carbon atoms,etc. Polymers which are also suitable for this use arepolyacrylonitriles, polyvinylpyridine and polyvinylpyrrolidine.

Inorganic supports (S) which can be used are, for example, solids wellknown as catalytic supports, such as the silicon, aluminium, magnesium,titanium and zirconium oxides and their mixtures. Amongst theseinorganic supports (S), the solids based on alumina and silica and theirmixtures are preferentially used.

The supports (S) used in this variant of the process according to theinvention must generally be inert towards the reagents used in thesynthesis of the catalytic solids based on titanium trichloride complexdescribed above. In order to do this, it may be preferable to subjectthem, before their use, to a heat treatment intended to remove alltraces of residual moisture therefrom.

The catalytic solids thus obtained have an appearance identical to thatof the supports used. Their porosity depends on the conditions for theirpreparation and on the nature of the support (S) introduced into thepreparation mixture.

The titanium trichloride content of the catalytic solids obtainedaccording to this variant of the process according to the invention isgenerally between about 7% and about 60% and the electron-donor compoundcontent is most often between about 1 and about 10% by weight relativeto the total weight of the catalytic solid.

This variant of the process for the preparation of the catalytic solidsaccording to the invention constitutes another means of controllingtheir porosity.

A second embodiment variant (b) consists in "prepolymerising" theparticles of catalytic solid based on titanium trichloride complex; this"prepolymerisation" treatment consists in bringing these particles intocontact with a lower alpha-monoolefin, such as ethylene, or, preferably,propylene, under polymerising conditions so as to obtain a solidcontaining in general between 5 and 500% by weight approximately of"prepolymerised" alpha-monoolefin. This "prepolymerisation" mayadvantageously take place on the particles resulting from the heattreatment of the liquid material in an optional inert hydrocarbondiluent as defined above, for a period sufficient to obtain the desiredamount of prepolymerised alpha-monoolefin on the solid.

A third embodiment variant (c) consists in subjecting the particles ofcatalytic solid based on titanium trichloride complex to a supplementaryactivating treatment with the aim of maintaining the stability of itsproperties and/or with the aim of increasing its stereospecificity. Thissupplementary activating treatment consists in bringing the particles ofcatalytic solid, preferably separated from the mixture in which theyhave been prepared, into contact with a supplementary activating agentchosen from organoaluminium compounds and the products of the reactionof an organoaluminium compound with a compound chosen fromhydroxyaromatic compounds in which the hydroxyl group is stericallyblocked. The organoaluminium compound is preferably chosen fromtrialkylaluminiums and alkylaluminium chlorides. The hydroxyaromaticcompound is preferably chosen from di-tert-alkylated monocyclicmonophenols and monoesters of3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionic acid, for examplen-octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate.

It is also possible to combine the variants (b) and (c) described above,that is to say to subject the particles of catalytic solidsimultaneously to the supplementary activating treatment and the"prepolymerisation" treatment described above.

Further details with regard to the supplementary activating treatmentdefined above, in particular with regard to the nature of theorganoaluminium and hydroxy-aromatic compounds, with the operatingconditions under which this treatment is carried out, will be found inthe patents BE-A-803875 (SOLVAY & Cie) and FR-A-2604439 (SOLVAY & Cie),the contents of which are incorporated by reference in the presentdescription.

For the polymerisation, the catalytic solid according to the inventionis used together with an activator chosen from the organometalliccompounds of metals of groups Ia, IIa, IIb and IIIb of the PeriodicTable (version published in Kirk-Othmer Encyclopedia of ChemicalTechnology, 2nd completely revised edition, volume 8, 1965, page 94) andpreferably from the compounds of formula:

    Al R'".sub.x Z.sub.3-x

where

R'" is a hydrocarbon radical containing from 1 to 18 carbon atoms andpreferably from 1 to 12 carbon atoms, chosen from alkyl, aryl,arylalkyl, alkylaryl and cycloalkyl radicals; the best results areobtained when R'" is chosen from alkyl radicals containing from 2 to 6carbon atoms;

Z is a halogen chosen from fluorine, chlorine, bromine and iodine; thebest results are obtained when Z is chlorine; and

x is any number such that 0<x≦3 and preferably such that 1.5≦x≦2.5; thebest results are obtained when x is 2.

Diethylaluminium chloride (DEAC) ensures a maximum activity and maximumstereospecificity of the catalytic system.

It is also possible to introduce a third constituent conventionallyknown to improve the stereospecificity of the catalytic system into thepolymerisation mixture, between the catalytic solid and the activatordefined above.

This third constituent may be chosen, for example, from ethers, esters,amides and organosilanes.

The catalytic systems thus defined apply to the polymerisation ofolefins which have terminal unsaturation and the molecule of whichcontains from 2 to 18 and preferably from 2 to 6 carbon atoms, such asethylene, propylene, 1-butene, 1-pentene, methyl-1-butenes, hexene, 3-and 4-methyl-1-pentenes and vinylcyclohexene. They are particularlyvaluable for the stereospecific polymerisation of propylene, 1-buteneand 4-methyl-1-pent-1-ene to form crystalline polymers which arestrongly or weakly isotactic. They also apply to the copolymerisation ofthese alpha-olefins with comonomers chosen from these non-identicalalpha-olefins and/or diolefins containing from 4 to 18 carbon atoms.Preferably, the diolefins are non-conjugated aliphatic diolefins, suchas 1,4-hexadiene, non-conjugated monocyclic diolefins, such as4-vinylcyclohexene, alicyclic diolefins having an endocyclic bridge,such as dicyclopentadiene, methylenenorbornene and ethylydenenorbornene,and conjugated aliphatic diolefins, such as butadiene or isoprene.

One advantage of the catalytic systems according to the invention isthat, if their porosity is sufficiently high, they permit theincorporation of a larger fraction of comonomers.

They also apply to the production of copolymers termed block copolymerswhich are made up from alpha-olefins and/or diolefins. These blockcopolymers consist of distinct blocks of variable compositions; eachblock consists of an alpha-olefin homopolymer or of a statisticalcopolymer comprising an alpha-olefin and at least one comonomer chosenfrom alpha-olefins and diolefins. The alpha-olefins and the diolefinsare chosen from those mentioned above.

The catalytic solids according to the invention are suitable for theproduction of propylene homopolymers and of copolymers containing intotal at least 50% by weight of propylene and preferably 60% by weightof propylene. They are particularly suitable for the production of blockcopolymers consisting of blocks of crystalline propylene homopolymer orstatistical copolymer containing at least 90% of propylene and blocks ofstatistical copolymer containing from 40 to 70 mol-% of propylene andfrom 60 to 30 mol-% of ethylene and relatively rich (more than 10% byweight and up to 70% by weight relative to the total weight of the blockcopolymer) in these latter blocks.

The polymerisation may be carried out by any known process: in solutionor in suspension in an inert hydrocarbon solvent or diluent, such asthose defined with respect to the preparation of the catalytic solid andwhich is preferably chosen from butane, pentane, hexane, heptane,cyclohexane, methylcyclohexane or their mixtures. It is also possible tocarry out the polymerisation in the monomer or one of the monomers keptin the liquid state or, alternatively, in the gas phase.

The use of the more porous catalytic solids according to the inventionis highly advantageous for the production of block copolymers rich inblocks of propylene and ethylene statistical copolymer defined above,especially in the gas phase polymerisation processes.

The catalytic systems according to the invention, in fact, allow largeamounts of statistical copolymer to be incorporated in the propylenehomopolymer.

Now, this statistical copolymer is generally an amorphous and stickyproduct which, if it is present in the free state and in a large amount,causes blocking and clogging of the polymerisation reactors and mainlydoes so in the gas phase processes. The use of the catalytic systemsaccording to the invention is therefore particularly advantageous inthese processes.

The polymerisation temperature is chosen generally between 20° and 200°C. and preferably between 50° and 90° C., the best results beingobtained between 65° and 85° C. The pressure is chosen generally betweenatmospheric pressure and 50 atmospheres and preferably between 10 and 30atmospheres. This pressure of course depends on the temperature used.

The polymerisation may be carried out continuously or discontinuously.

The preparation of the copolymers termed block copolymers may also becarried out by known processes. It is preferred to use a two-stepprocess consisting in polymerising an alpha-olefin, generally propylene,by the method described above for homopolymerisation. Subsequently, theother alpha-olefin and/or diolefin, generally ethylene, is polymerisedon the same catalytic site. This second polymerisation may be carriedout after having completely or partially removed the monomer which hasnot reacted during the first step.

The organometallic compound and the catalytic solid may be addedseparately to the polymerisation mixture. It is also possible to bringthem into contact at a temperature between -40° and 80° C. for a periodwhich is dependent on this temperature and which may range from one hourto several days, before introducing them into the polymerisationreactor.

The total amount of organometallic compound used is not critical; it isgenerally more than 0.1 mmol per liter of diluent, of liquid monomer orof reactor volume, preferably more than 0.5 mmol per liter.

The amount of catalytic solid used is determined as a function of itsTiCl₃ content. It is generally chosen such that the concentration of thepolymerisation mixture is higher than 0.01 mmol of TiCl₃ per liter ofdiluent, of liquid monomer or of reactor volume, and preferably higherthan 0.05 mmol per liter.

The ratio of the amounts of organometallic compound and of catalyticsolid is also not critical. It is generally chosen such that the molarratio of organometallic compound/TiCl₃ present in the solid is between0.5 and 20 and preferably between 1 and 15. The best results areobtained when the molar ratio is between 2 and 12.

The molecular weight of the polymers produced by the process of theinvention may be controlled by the addition of one or more molecularweight-controlling agents, such as hydrogen, diethylzinc, alcohols,ethers and alkyl halides, to the polymerisation mixture.

The following examples serve to illustrate the invention.

The meaning of the symbols used in these examples, the units expressingthe quantities mentioned and the methods for determination of thesequantities are explained below.

IPV=internal pore volume of the catalytic solid recorded in the zone ofpore radii between 1000 and 15000 Å and expressed in cm³ /g.

D_(m) =average diameter of the catalytic solid particles in μm.

FPV=total pore volume of the solid polymer collected, expressed in cm³/g.

SPV=total pore volume of the support (S), expressed in cm³ /g.

Ss=specific surface area of the catalytic solid, expressed in m² /g(British standard BS 4359/1).

Ssu=specific surface area of the support (S), expressed in m² /g(British standard BS 4359/1).

α=catalytic activity conventionally expressed as grams of polymerinsoluble in the polymerisation mixture, obtained per hour and per gramof TiCl₃ contained in the catalytic solid. This activity is assessedindirectly from the determination of the residual titanium content inthe polymer by X-ray fluorescence.

ASW=apparent specific weight of the insoluble polymer fraction,expressed in g/dm³.

fTri=isotacticity index of the polymer, determined from the molarfraction of isotactic triads (block chain of three propylene monomerunits in meso configuration) in the total polymer. This value isdetermined by ¹³ C nuclear magnetic resonance as described inMacromolecules, volume 6, No. 6, page 925 (1973) and in references (3)to (9) of this publication.

MFI=melt flow index determined under a load of 2.16 kg at 230° C. andexpressed in g/10 min (ASTM standard D 1238).

G=torsional rigidity modulus of the polymer, determined at 100° C. andfor a torsion angle of 60° arc, the temperature of the mould being fixedat 70° C. and the conditioning time at 5 minutes (standards BS 2782 -Part I - method 150A; ISO 458/1, method B; DIN 53447 and ASTM D 1043).This modulus is expressed in daN/cm².

Et=ethyl radical C₂ H₅.

Isoamyl=isoamyl radical (CH₃)₂ CH--CH₂ --CH₂ --

The average diameter of the catalytic solid particles is estimated byobservation of this solid as a suspension in decalin under an opticalmicroscope (magnification 200).

The porosity of the catalysts and that of the polymers obtained in thepolymerisation tests described below are determined by the mercurypenetration method using porosimeters marketed by Carlo Erba Co. in thezone of pore radii between 75 and 75000 Å.

The ethylene content of the block copolymers is obtained from thecharacteristic signals of these units observed by ¹³ C nuclear magneticresonance as described in Rubber Chemistry and Technology, volume 44(1971), page 781 et seq.

EXAMPLES 1 TO 3 A--Preparation of the Catalytic Solids

1--Preparation of the compositions (C)

80 ml of a dry mixture of aliphatic hydrocarbons boiling at 175° C.(marketed under the name Isopar H by EXXON CHEMICALS) and 17 ml (136mmol) of diethylaluminium chloride (DEAC) are introduced, under anitrogen atmosphere, into a 200-ml reactor fitted with a single-bladestirrer rotating at 400 rev/min.

While keeping the temperature of this solution below 50° C., a chosenamount of isoamyl alcohol, as indicated in Table I below, is addeddropwise thereto. Stirring of the solution is continued for 20 hours atambient temperature before the solution is used.

The compositions (C) may be represented by the empirical formulaAlEt_(p) (Oisoamyl)_(q) Cl, for which the values of the numbers p and q,corresponding to the molar ratios between the various constituents, areindicated in Table I.

2--Synthesis of the catalytic solids

100 ml of Isopar H and 15 ml of TiCl₄ are introduced into a 1-1autoclave fitted with a single-blade stirrer rotating at 250 rev/min andpreviously purged with nitrogen.

Keeping this solution at 30° C., 69 ml (340 mmol) of diisoamyl ether(DIAE) are added thereto in the course of 30 minutes. Following thisaddition, 97 ml of a composition (C) as described in Table I, which isequivalent to 136 mmol of aluminium, are introduced into the"pretreated" TiCl₄ within half an hour. Finally, 45 ml of TiCl₄ areadded in the course of about 10 minutes, while increasing thetemperature so as to attain 100° C. after 1 hour. The first solidparticles appear during this heat treatment.

The reaction mixture, consisting of a suspension of particles, is keptat this temperature for 2 hours (ageing) and then brought back toambient temperature.

The liquid phase is then separated off from the catalytic solid bydecanting and the solid product (about 45 g) is washed with hexane bysuccessive decanting and then dried for 2 hours under a stream ofnitrogen at 70° C.

The characteristics of these catalytic solids, which are purplish-bluein colour, are also given in Table I below.

The solid particles are in the form of spheroid agglomerates of finergrains arranged in groups.

B--Polymerisation of Propylene in Suspension in the Liquid Monomer inthe Presence of the Catalytic Solids (Reference Conditions)

The following are introduced into a previously dried 5-1 autoclave,while sweeping with dry nitrogen:

400 mg of DEAC (in the form of a 200 g/l solution in hexane) marketed bySCHERING, the Cl/Al atomic ratio of which is adjusted to 1.02 by theaddition of ethylaluminium dichloride;

50 mg of catalytic solid (the molar ratio between the DEAC and the TiCl₃present in the solid is then about 10);

hydrogen under a partial pressure of about 1 bar; and

3 l of liquid propylene.

The reactor is kept at 65° C., with stirring, for 3 hours. The excesspropylene is then degassed and the polypropylene (PP) formed, which isin the form of grains of uniform morphology, is recovered.

The results obtained during the polymerisation experiments with thevarious catalytic solids are also given in Table I below.

                  TABLE I                                                         ______________________________________                                                        Examples                                                                      1      2        3                                             ______________________________________                                        Preparation of the                                                            compositions (C)                                                              Volume of alcohol (ml)                                                                          3.75     7.5      9                                         Empirical formula AlEt.sub.p                                                  (Oisoamyl).sub.q Cl                                                           p                 1.75     1.5      1.4                                       q                 0.25     0.5      0.6                                       Characterisation of the                                                       catalytic solids                                                              TiCl.sub.3 content (g/kg)                                                                       805      773      770                                       Aluminium content (g/kg)                                                                        1        1.2      1.3                                       DIAE content (g/kg)                                                                             95       78       62                                        IPV               0.043    0.06     0.08                                      Ss                172      174      90                                        D.sub.m           15-20    10-20    15-25                                     Polymerisation results                                                        Activity α  4810     3835     2200                                      ASW               366      378      318                                       fTri              91.8     91       93                                        G                 605      515      --                                        MFI               17.2     2.9      25.1                                      FPV               0.06     0.1      0.17                                      ______________________________________                                    

It is thus found that, all other things being equivalent, variablecontents of groups Y in the composition (C) enable the internal porosityof the catalytic solids to be controlled to a large extent. Moreparticularly, an increase in the intermediate pore volume for the poreradii between 1000 and 15000 Å (IPV) in parallel with the increase inthe group Y content is observed.

EXAMPLES 4R AND 5R

These examples 4R and 5R are given by way of comparison.

EXAMPLE 4R

100 ml of Isopar H and 15 ml (136 mmol) of TiCl₄ are introducedsuccessively, with stirring (single-blade stirrer rotating at 250rev/min), into a 1-1 dry autoclave kept at 30° C. under a nitrogenatmosphere. 69 ml (340 mmol) of diisoamyl ether are then added in thecourse of 30 minutes. Following this addition, a solution consisting of80 ml of Isopar H and 17 ml of DEAC is introduced dropwise in the courseof half an hour. Finally, while progressively (in the course of 1 hour)raising the temperature of the solution up to 100° C., 45 ml (408 mmol)of TiCl₄ are added in the course of 10 minutes. The reaction mixture iskept at this temperature for 2 hours and then brought back to ambienttemperature, washed with hexane and dried using dry nitrogen and heat.This solid contains, per kg: 635 g of TiCl₃, 12 g of aluminium and 10 gof DIAE; its IPV is 0.29 cm³ /g and its Ss is 140 m² /g.

A polymerisation experiment is carried out in the presence of thiscatalytic solid under conditions strictly identical to those describedin Example 1, part B. At the end of this experiment, 115 grams ofpolymer (α=1280) are recovered, this polymer being in the form of grainsof irregular morphology and having an ASW of only 205 g/dm³.

EXAMPLE 5R

A catalytic solid based on TiCl₃ is prepared as described in Example 1but using the composition (C) described below.

The composition (C) is obtained by mixing 80 ml of Isopar H, 8.5 ml (68mmol) of DEAC and 22.75 ml (136 mmol) of dibutyl ether (DBUE).

The catalytic solid contains 799 g/kg of TiCl₃, 1.3 g of aluminium and86 g of DIAE; its IPV is 0.26 cm³ /g.

The polymerisation experiment (conditions: Example 1, part B) permitsthe production, with an activity α of only 1190, of a polymer for whichthe isotacticity index determined by NMR is only 86%.

EXAMPLES 6 AND 7

Catalytic solids are prepared as in Example 1 except in respect of theaddition of TiCl₄.

In Example 6, the heat treatment of the liquid material resulting fromthe contact between the "pretreated" TiCl₄ and the solution (C) takesplace after the addition of all of the TiCl₄.

In Example 7, all of the TiCl₄, that is to say 60 ml, is introduced as asingle amount from the start of the synthesis of the catalytic solid.

The characteristics of these solids and the results of thepolymerisation experiments are collated in Table II below.

                  TABLE II                                                        ______________________________________                                                          Examples                                                                      6      7                                                    ______________________________________                                        Properties of the catalytic solids                                            TiCl.sub.3 content (g/kg)                                                                         860      776                                              Aluminium content (g/kg)                                                                          0.8      1.2                                              DIAE content (g/kg) 85       71                                               IPV                 0.06     0.06                                             Ss                  159      176                                              Polymerisation results                                                        Activity α    3835     3700                                             ASW                 376      375                                              fTri                90       92                                               G                   540      625                                              MFI                 4.2      10.4                                             FPV                 0.11     0.09                                             ______________________________________                                    

EXAMPLE 8

The catalytic solid is prepared using the method described in Examples 1to 3, part A, paragraph 2, using the composition (C) obtained asdescribed below.

80 ml of Isopar H and 18.5 ml of triethylaluminium (TEAL) are introducedsuccessively into a 200-ml reactor previously purged with dry nitrogen.While keeping this solution at a temperature below 50° C., 22.5 ml ofisoamyl alcohol are added dropwise. The empirical formula of thiscomposition is: AlEt₁.5 Oisoamyl₁.5.

The catalytic solid contains 764 g/kg of TiCl₃, 1 g of aluminium and 71g of DIAE; its IPV is 0.09 cm³ /g and its specific surface area is 51cm² /g.

Used in the test for the polymerisation of propylene in a condensedmedium, it leads, with an activity α of 2835, to a polypropylene havingan ASW of 362, an MFI of 7.6, a G of 535 and an isotacticity indexdetermined by NMR of 88%. The FPV of the solid polymer is 0.09.

EXAMPLE 9

This example illustrates a variant of the synthesis of the composition(C).

80 ml of Isopar H, 102 mmol (12.7 ml) of DEAC and 34 mmol ofchloroethoxyethylaluminium are introduced successively, under a nitrogenatmosphere, into a previously dried reactor in order to obtain acomposition of empirical formula AlEt₁.75 OEt₀.25 Cl.

This solution is added to the "pretreated" TiCl₄ solution as describedin Examples 1 to 3, part A, paragraph 2, in order to form apurplish-blue catalytic solid containing 792 g of TiCl₃, 0.8 g ofaluminium and 63 g of DIAE per kg of solid and having a IPV and Ss of,respectively, 0.061 cm³ /g and 165 m² /g.

The D_(m) of the catalyst grains is between 15 and 20 μm.

The polymerisation test (reference conditions) allows the production of350 g of polymer (activity α of 3230) having the followingcharacteristics:

ASW=340 g/dm³

fTri=94.8%

G=700 daN/cm²

MFI=3 g/10 min

FPV=0.12 cm³ /g

EXAMPLE 10

A composition (C) of empirical formula AlEt₁.65 (OEt)₀.35 Cl is obtainedby reacting 17 ml of DEAC with 3 ml of ethanol using the methoddescribed for Example 1.

The production of the catalytic solid, identical to that described inExample 1, leads to a violet solid containing, per kg, 879 g of TiCl₃,0.9 g of aluminium and 127 g of DIAE.

The IPV is 0.067 cm³ /g.

Used in the propylene polymerisation test, under the referenceconditions, this catalytic solid leads to the production, with anactivity α of 4060, of a polymer which has an ASW of 358 and an FPV of0.1 cm³ /g. The other characteristics of the polypropylene are:fTri=92%; MFI=3.8 and G=546.

EXAMPLE 11 A--Preparation of the Catalytic Solid

1--Preparation of the composition (C)

800 ml of Isopar H and 170 ml of DEAC are introduced successively, undera nitrogen atmosphere, into a 2-1 reactor fitted with a single-bladestirrer rotating at 400 rev/min. Subsequently 82 ml of isoamyl alcoholare introduced dropwise (in the course of one hour) while keeping thetemperature of the solution below 50° C.

The solution is stored at ambient temperature, with stirring and whilesweeping with nitrogen, for 16 hours before it is used.

This composition may be characterised by the empirical formula: AlEt₁.45(Oisoamyl)₀.55 Cl.

2--Synthesis of the catalytic solid

1 l of Isopar H and 150 ml of TiCl₄ are introduced into a 5-1 dryreactor fitted with a single-blade stirrer rotating at 220 rev/min.Keeping this TiCl₄ solution at 30° C., 690 ml of DIAE are introducedslowly (30 minutes), followed by 970 ml of the composition (C) describedabove. The introduction of the composition (C) is carried out in thecourse of 60 minutes. After having reduced the stirring speed to 85rev/min, 450 ml of TiCl₄ are introduced in the course of 20 minutes,while raising the temperature in order to attain 100° C. after 50minutes. The suspension is kept at 100° C. for 2 hours and the solidformed is isolated by settling and then washed 7 times with 2 l of dryhexane.

This catalytic solid, of purplish-blue colour, contains, per kg, 830 gof TiCl₃, 1 g of aluminium and 58 g of DIAE. Its IPV is 0.07.

3--Prepolymerisation of the catalytic solid

All of the catalytic solid obtained according to point 2 (that is to sayabout 317 g of solid based on TiCl₃ complex) is suspended in 1.8 l ofhexane at 30° C., while stirring at 150 rev/min.

780 ml of a hexane solution of a preactivating agent (hereinafter termedpreactivating agent D), previously prepared by mixing, per liter ofhexane, 80 g of DEAC and 176 g of n-octadecyl3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate marketed under thename IRGANOX 1076 by CIBA-GEIGY, are introduced slowly (30 minutes).This solution is used 15 minutes after the end of the evolution of gasobserved during its preparation.

Following this addition, 240 ml of propylene are introduced in thecourse of 30 minutes and stirring of the suspension is continued for afurther 30 minutes.

After settling, the resulting prepolymerised catalytic solid is washed 7times using 2 l of dry hexane, the solid being resuspended after eachwashing, and then dried by sweeping with nitrogen in a fluidised bed for2 hours at 70° C.

The preactivated catalytic solid contains, per kg, 533 g of TiCl₃, 8.2 gof aluminium, 18 g of DIAE, 228 g of polypropylene and an amount ofpreactivating agent D estimated at 142 g. The IPV of the catalyst is0.09 cm³ /g and its specific surface area is 8 m² /g.

B--Polymerisation of Propylene in the Gaseous Monomer

The preactivated catalytic solid is used in an experiment for thepolymerisation of propylene comprising a first step carried out in theliquid monomer and a second step carried out in the gas phase under theoperating conditions detailed below.

The following are introduced, under a stream of nitrogen, into a 5-1autoclave used according to Example 1, part B:

342 mg of an activating agent consisting of a mixture of DEAC as usedabove with triethylaluminium and ethyl benzoate (EB). The molar ratiosof DEAC/EB and TEAL/EB are, respectively, 60/1 and 2.2/1.

35 mg of prepolymerised catalytic solid (the molar ratio between theDEAC and the TiCl₃ present in the solid is then about 15).

An absolute pressure of 2 bars of hydrogen is then produced in theautoclave, 1 l of liquid propylene is then introduced, with stirring,and the temperature is raised to 50° C. Polymerisation is carried outunder these conditions for 10 minutes. The autoclave is then degassed toa pressure of 7 bars absolute, while being heated to 75° C. An absolutehydrogen pressure of 0.8 bar is then produced therein and propylene isthen introduced in the gas state until a total pressure of 21 barsabsolute at the temperature under consideration is reached. Afterpolymerisation under these conditions for 4 hours, the reaction isstopped by the introduction of 25 ml of a 1 mol/l sodium hydroxidesolution and, after washing the polymer with 2 l of water, 214 g of drypolymer are recovered.

The activity of the catalytic solid is then 1820 and the productivity is7280 g of polypropylene (PP) per gram of preactivated catalytic solid.This PP has an MFI of 14.8, a fTri of 97 and an FPV of 0.15 cm³ /g.

EXAMPLE 12

The prepolymerised catalytic solid described in Example 11 is used in atwo-step polymerisation experiment which has the aim of producing ablock copolymer by the method described below.

The following are introduced, under a stream of nitrogen, into a 5-1autoclave used according to Example 1, part B:

342 mg of an activating agent consisting of a mixture of DEAC as usedabove with triethylaluminium and ethyl benzoate (EB). The molar ratiosof DEAC/EB and TEAL/EB are, respectively, 60/1 and 2.2/1.

35 mg of preactivated catalytic solid (the molar ratio between the DEACand the TiCl₃ present in the solid is then about 15).

An absolute pressure of 2 bars of hydrogen is then produced in theautoclave, 1 l of liquid propylene is then introduced, with stirring,and the temperature is raised to 50° C. Polymerisation is carried outunder these conditions for 10 minutes. The autoclave is then degassed toa pressure of 7 bars absolute, while being heated to 75° C. An absolutehydrogen pressure of 0.6 bar is then produced therein and propylene isthen introduced in the gas state until a total pressure of 21 barsabsolute at the temperature under consideration is reached. Afterpolymerisation for 2 hours, the autoclave is degassed to 4.5 barsabsolute while keeping the temperature at 75° C. In a first step,gaseous propylene is introduced therein so as to ensure a total pressurein the autoclave of 15.4 bars at the temperature under consideration andgaseous ethylene is then introduced to obtain a total pressure of 21bars absolute. The propylene is copolymerised with the ethylene for 140minutes while continuously feeding the autoclave with a gaseous mixtureof propylene and ethylene having the composition of the copolymerformed, so as to keep the composition of the polymerisation mixtureconstant.

The polymerisation is stopped by the introduction of 25 ml of a 1 mol/lsodium hydroxide solution and, with an activity α of 1433, 360 g ofpolymer are recovered, which polymer has a good pourability and thefollowing characteristics:

MFI=0.61

G=185

FPV=0.04

The proportion of elastomer in the total polymer is 59% by weight; theethylene content of the total polymer is 265 g/kg.

EXAMPLE 13

This example illustrates a variant of the synthesis of the composition(C).

The catalytic solid is prepared as in Example 1 but by replacing the 7.5ml of isoamyl alcohol by 8.5 ml of 3-methylbutane-1-thiol.

The characterisation of the catalytic solid and that of thepolypropylene obtained in a reference experiment are described in TableIII below.

                  TABLE III                                                       ______________________________________                                        Properties of the catalytic solids                                            TiCl.sub.3 content (g/kg)                                                                          847                                                      Aluminium content (g/kg)                                                                           0.7                                                      DIAE content (g/kg)  90                                                       IPV                  0.095                                                    Ss                   90                                                       Polymerisation results                                                        Activity α     1970                                                     ASW                  310                                                      fTri                 92                                                       MFI                  6.1                                                      FPV                  0.07                                                     ______________________________________                                    

EXAMPLES 14 TO 17

These examples illustrate the preparation of catalytic solids in thepresence of an organic or inorganic support (S).

A--Preparation of the Catalytic Solids

1--Preparation of the compositions (C)

30 ml of Isopar H and 5.7 ml of DEAC are introduced into a 100-ml flaskpreviously conditioned under nitrogen. While continuing to stir thissolution at 40° C., 1.2 ml of isoamyl alcohol are added dropwise theretoin the course of about 30 minutes. Stirring of the solution thusobtained is continued for 12 hours before it is used.

2--Synthesis of the catalytic solids

The nature and the amount of the supports (S) used in these syntheses,their characteristics and the heat treatments to which they weresubjected beforehand are given in Table IV below.

160 ml of Isopar H, 23 ml of diisoamyl ether and the chosen amount (asindicated in Table IV) of support (S) are introduced successively into a1-liter autoclave fitted with a single blade stirrer rotating at 250rev/min and previously purged with nitrogen. 20 ml of TiCl₄ are thenadded to this suspension in the course of 30 minutes.

While keeping this suspension at 30° C., 35.7 ml of the composition (C)described above are added thereto within 1 hour. The temperature is thenraised so as to attain 100° C. after 1 h.

The reaction mixture is kept at this temperature for 2 hours and thenbrought back to ambient temperature.

The liquid phase is then separated from the catalytic solid by decantingand the solid product is washed with hexane by successive decanting andthen dried for 1 hour under a stream of nitrogen at 70° C.

The catalytic solid thus obtained has an appearance identical to that ofthe support; its colour is violet. Table IV below also gives thecharacteristics of the catalytic solids obtained as well as theirperformance in the polymerisation test in the liquid monomer under thereference conditions (Example 1, part B).

                  TABLE IV                                                        ______________________________________                                                Examples                                                                      14     15        16        17                                         ______________________________________                                        Characteristics                                                               of the supports                                                               (S)                                                                           type               silica    alumina polymer*                                 trade name                                                                              SG 532   SAEHS     KETJEN  CHROMO-                                                     33-50     13      SORB 101                                 company   GRACE    CARBOR-   AKZO    Jhons-                                                      UNDUM             Manville                                                                      Co Ltd                                   SPV       0.6      0.33      1       0.9                                      Ssu       320      3         301     41                                       Heat treatment                                                                of the support                                                                (S)                                                                           Temperature                                                                             800      800       800     80                                       (°C.)                                                                  time (h)  16       16        16      1                                        Amount of                                                                     support (S)                                                                   used                                                                          (g)       25       90        25      25                                       Characteristics                                                               of the catalytic                                                              solids                                                                        TiCl.sub.3 content                                                                      363      134       350     118                                      (g/kg)                                                                        DIAE content                                                                            89       16        50      46                                       (g/kg)                                                                        IPV       0.01     0.10      0.12    0.05                                     Ss        243      33        204     --                                       Dm        20-200   10-150    --      --                                       Polymerisation                                                                results                                                                       Activity α                                                                        2800     3980      3450    3340                                     ASW       395      359       442     330                                      fTri      89       90        90      91                                       G         445      500       575     --                                       MFI       2.9      4.1       6.1     4                                        FPV       0.08     0.30      0.12    0.14                                     ______________________________________                                         *comprising a styrene/divinylbenzene copolymer                           

We claim:
 1. A catalytic solid for the stereospecific polymerisation of alpha-olefins, obtained by heat treatment, in the presence of a halogenated activating agent, of a liquid material prepared by contacting TiCl₄, pretreated with an electron-donor compound, with a composition (C) of the formula

    AlR.sub.p (Y) .sub.q X .sub.3-(p+q)                        (I)

in which R represents a hydrocarbon radical; Y represents a group chosen from --OR', --SR' and --NR'R", in which R' and R" each represent a hydrocarbon radical or a hydrocarbon atom; X represents a halogen; p is an arbitrary number such that 0<p<3; and q is an arbitrary number such that 0<p<3; the sum (p+q) being such that 0<(p+q)≦3 to precipitate a catalytic solid comprising a titanium trichloride complex.
 2. The catalytic solid according to claim 1, wherein in formula (I):R represents a straight-chain or branched alkyl radical containing from 2 to 8 carbon atoms; Y represents a group --OR', in which R' is chosen from straight-chain or branched alkyl radicals containing from 1 to 12 carbon atoms and aryl radicals containing from 6 to 35 carbon atoms; X represents chlorine; p is a number such that 1≦p≦2; and q is a number such that 0.1≦q≦3.
 3. The catalytic solid according to claim 1, wherein the electron-donor compound is chosen from aliphatic ethers.
 4. The catalytic solid according to claim 1, wherein the halogenated activating agent is chosen from inorganic halogenated compounds.
 5. The catalytic solid according to claim 4, wherein the halogenated activating agent is TiCl₄.
 6. The catalytic solid according to claim 1, including adding an organic or inorganic support (S) at any time to the mixture for the preparation of the said solid.
 7. The catalytic solid according to claim 6, wherein the support (S) is added before the heat treatment of the liquid material.
 8. The catalytic solid according to claim 6, wherein the support (S) is a preformed organic polymer.
 9. The catalytic solid according to claim 6, wherein the support (S) is an oxygen-containing compound.
 10. A process for the preparation of a catalytic solid for the stereospecific polymerisation of alpha-olefins, comprising subjecting a liquid material prepared by contacting TiCl₄, pretreated with an electron-donor compound, with a composition (C) corresponding to the general formula

    AlR.sub.p (Y) .sub.q X .sub.3-(p+q)                        (I)

in which R represents a hydrocarbon radical; Y represents a group chosen from --OR', --SR' and --NR'R", in which R' and R" each represent a hydrocarbon radical or a hydrogen atom; X represents a halogen; p is an arbitrary number such that 0<p<3; and q is an arbitrary number such that 0<q<3; the sum (p+q) being such that 0<(p+q)≦3, to a heat treatment carried out in the presence of a halogenated activating agent to precipitate a catalytic solid comprising a titanium trichloride complex.
 11. The process according to claim 10, wherein the amount of composition (C) brought into contact with the pretreated TiCl₄ is such that the atomic ratio between the aluminium contained in the composition (C) and the titanium contained in the pretreated TiCl₄ is between 0.1 and
 8. 12. The process according to claim 10, wherein the heat treatment is carried out under conditions inducing the substantial precipitation of solid particles comprising titanium trichloride.
 13. The process according to claim 10, wherein the halogenated activating agent is added at the start of the heat treatment.
 14. The process according to claim 10, wherein the halogenated activating agent is TiCl₄ originating from a non-reduced excess of the initial TiCl₄.
 15. The process according to claim 10, wherein the amount of activating agent used is between 0.5 and 10 mol per mole of titanium trichloride present in the liquid material.
 16. The process according to claim 10, wherein the heat treatment is followed by ageing.
 17. The process according to claim 10, wherein an organic or inorganic support (S) is added at any time to the mixture for the preparation of the said solid.
 18. The catalytic solid according to claim 9 wherein said oxygen-containing compound is selected from the group consisting of oxides of silicon, aluminum, magnesium, titanium, and zirconium, and mixtures thereof. 